Enantioselective construction of molecules bearing multiple stereogenic elements is increasingly related to the synthesis of enantiopure natural products, pharmaceuticals, and functional materials. However, atom‐economical and enantioselective approaches to install multiple stereogenic elements in a small molecular template by limited chemical transformation remain challenging. We describe an organocatalytic enantioselective method for the preparation of polychiral molecules bearing four types of stereogenic elements in fused azepines via vinylidene ortho‐quinone methide (VQM)‐mediated intramolecular electrophilic aromatic substitution. This method was proved robust with a wide range of substrate scope (46–92 % yield), with excellent diastereoselectivity (>20:1 dr) and enantioselectivity achieved (up to 97 % ee). Optical properties and Ru3+‐induced fluorescence responses of these compounds suggest their potential applications in optoelectronic materials and heavy metal ion detection.

We herein demonstrated an efficient method for the atroposelective construction of nine-membered carbonate-bridged biaryls through vinylidene orthoquinone methide (VQM) intermediates. Diverse products with desirable pharmacological features were synthesized in satisfying yields and good to excellent enantioselectivities. In subsequent bioassays, several agents showed considerable antiproliferative activity via the mitochondrial-related apoptosis mechanism. Further transformations produced more structural diversity and may inspire new ideas for developing functional molecules.

We herein demonstrated an efficient method for the atroposelective construction of nine-membered carbonate-bridged biaryls through vinylidene orthoquinone methide (VQM) intermediates. Diverse products with desirable pharmacological features were synthesized in satisfying yields and good to excellent enantioselectivities. In subsequent bioassays, several agents showed considerable antiproliferative activity via the mitochondrial-related apoptosis mechanism. Further transformations produced more structural diversity and may inspire new ideas for developing functional molecules.

A palladium‐catalyzed tandem cyclization of 2‐(2‐ethynylphenyl)acetonitriles with isocyanides has been developed. Various indeno[2,1‐b]pyrroles were prepared in 55%–82% yields under air atmosphere at 100 °C. The key to the success of this protocol is construction of new C−C and C−N bonds via the orderly insertion of isocyanides.

We report herein an organocatalytic asymmetric protocol for the construction of tetrasubstituted carbon stereocenters bearing three heteroatoms. The reaction proceeded via the enantioselective intramolecular cyclization reaction of vinylidene ortho-quinone methide (VQM) with imidates to form pentacyclic heterocycles. The formed tetrasubstituted carbon center was stable under a high temperature and the conditions for further transformations.